Tertiary aminomethylbenzenes



Patented Get. 7, 1952 TERTIARY AMINOMETHYLBENZENES- JohnO. Van Hook, Roslyn, and Willard J. Croxall, Bryn Athyn Pa assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No'Drawing. Application June 29, 194:9, Serial N- 102,163

This invention deals with tertiary tris( aminomethyl) benzenes and with a method 'for the preparation of these new compounds.

They are prepared by the trimerization of tertiary propargylamines, which is effected by heating these amines at 50 to 120 0., preferably at 60 to 80 C., in the presence of a nickel carbonylphosphine or nickel carbonyl-arsine catalyst. The trimerization reaction is best effected in an inert, organic solvent, such as benzene, toluene, xylene, petroleum ether, or low boiling naphtha.

As catalyst, there is preferably used a nickel carbonyl-triphenyl phosphine catalyst, although other trisubstituted phosphines may be used in place of the triphenyl phosphine with lower yields. There may also be used a nickel carbonyltriphenyl arsine catalyst. To prepare the catalyst, a solution of nickel carbonyl in an inert, organic solvent and triphenyl phosphine or triphenyl arsine, usually also in such a solvent, are mixed in the proportion of one mole of nickel carbonylto one to two moles of one of the latter. In place of the phenyl group there may be used an alkylphenyl group or other neutrally substituted phenyl group. Carbon monoxide is slowly evolved and there is formed a catalyst which corresponds in composition to Ni(CO)4:r'(MAI3)a:, when M is an element of group V-B of the periodic table having an atomic weight from 31 to 75, a: has a value of one to two, and Ar is a phenyl group. The catalyst is best used. in the solution in whichit is prepared. The amount of catalyst required is small, varying from 0.25% to 5% of the weight of the tertiary propargylamine. The preferred amount of catalyst used is 1% to 2 of the weight of such amine.

The tertiary propargylamines are available through thereaction of secondary amines, aldeof a heavy metal of the first or second groups of the usual periodic table. In particular, copper and its salts such as cuprous chloride, copper acetate or form'ate are effective as catalysts in promoting the condensation of secondary amine, aldehyde .or. ketone, and acetylene. Temperatures up to 120 C. may be used, depending upon the particular combination of reactants, and the 6 Claims. (01. 260--247) hydes or ketones, and acetylene in the presence NCHzCECH C4110 CH2 7 nomcscn OBHU ' NCHZCEOH CHzCHfl Nomczon QHzCHz OHzCH:

C. 2 NCHECECH and .C 2CH2 O NCHZCECH These are obtained by the condensation ofthe corresponding secondary amine, formaldehyde, and acetylene. Other .aldehydes may, however,

'bejused and simple ketones may replace the aldehyde. Thus, acetaldehyde, propionaldehyde, bu-

tyraldehyde, heptaldehyde, 2-ethy1 hexaldehyde, 3,3,5-trimethyl hexaldehyde, benzaldehyde, hexahydrobenzaldehyde, 2-ethylpropylacrolein, acetone, methyl ethyl ketone, and methyl hexyl ketone are effective components in this reaction. Typical of the 'propargylamines thus prepared are i (CHOZ'NEGE o H Q Ha CHmNl CECE 'i-QHslzNo CECE iHt (O HMNOHCECH CHzCHiI O NCHCECH CHzCHa H:

CH3 (CHOzNCEOH (CHa)zNCHCECH (CH5)2NCHCECH eHu (CHs)zNCHCECH These amines fall within the general formula where R and R are monovalent hydrocarbon groups when taken individually, particularly alkyl groups, and, when taken together, R and R represent a saturated divalent chain which forms a fiveto six-sided heterocycle with the nitrogen, and R and R represent hydrogen or a monovalent hydrocarbon group. ypical monovalent hydrocarbon groups for R and R are alkyl groups, representative of which are methyl, ethyl, propyl, butyl, amyl, hexyl, h-eptyl, octyl, and decyl, unsaturated aliphatic hydrocarbon groups, such as allyl, methallyl, and crotyl, cycloaliphatic groups, such as cyclohexyl and methylcyclohexyl, aralkyl groups, such as benzyl, methylbenzyl, and phenylethyl, and aryl groups such as phenyl. It is preferred that the total number of carbon atoms in R and R be not in excess of twelve. The two groups R and R may be the same or different. Typical mixed combinations are methyl and benzyl, methyl and cyclohexyl, methyl and butyl, methyl and nonyl, methyl and allyl, methyl and phenyl, and the like. When R and R together represent a divalent chain which forms a heterocycle with the nitrogen, they thus represent the groups as found in pyrrolidine, piperidine, morpholine and thiamorpholine respectively. It will be recognized that these are all secondary amines and undergo the same reaction with an aldehyde or ketone and acetylene as other secondary amines such as dimethylamine, diisopropylamine, dibutylamine, diamylamine, benzylmethylamine, dicyclohexylamine, methylhexylamine, diallylamine, methylisononylamine, methylaniline, and the like. Furthermore, such amines as diethanolamine can be used for preparation of a propargylamine, thus supplying hydroxyethyl groups as R and R.

When an aldehyde is used in the preparation of the tertiary propargylamine, at least one of the groups R and R" is hydrogen. When formaldehyde is used, both R and R" are hydrogen. With other aldehydes, such as acetaldehyde, propaldehyde, butyraldehyde, heptaldehyde and nonaldehyde or benzaldehyde, and alkyl benzaldehydes, such as methylbenzaldehyde or butylbenzaldehyde, and tetrahydrobenzaldehyde or hexahydrobenzaldehyde, one is hydrogen and the other is a hydrocarbon group. In the case where weighed 92 g.

an aliphatic ketone is used as a reactant in the formation of propargylamines, R and R are both monovalent hydrocarbon groups, such as methyl or methyl and ethyl or methyl and hexyl or isopropyl. It is preferred that R and R" contain a total of not over eleven carbon atoms.

The tertiary propargylamines trimerize under the influence of a catalyst, Ni(CO)4-a;'(MAr3):c, where M, Ar, and a: have the above-defined meanings. Unreacted propargylamine and solvent may be separated and, where the various R substituents are not too large, the product may be distilled under reduced pressure. Ordinary vacuum distillation is usually effective with R substituents up to a total of about fifteen carbon atoms. Short path and flash distillation methods may be applied where somewhat larger groups occur.

With still larger R substituent it may be necessary to treat the product as residue by such known methods as charcoaling and extraction.

The products obtainedare of the general formula where R, R, R, and R have the meanings described above. They are useful in bactericidal and fungicidal compositions, a basic reagents for overcoming acidity, as catalysts, as inhibitors against oxidation and corrosion, serving as additives, for example, in oils and greases. They form salts with acids and quaternary ammonium compounds with alkylating agents and as such find use for wetting, emulsifying, and dispersing. Reaction by addition can occur with alcohols, mercaptans, and other compounds with active hydro gen atoms. Some of the above amines have marked insecticidal action.

Preparation of typical compounds of thi invention is illustrated in the following examples.

EXAMPLE 1 1,3,5-tris (dimethylaminomethyl) benzene was filtered to remove about two grams of a black tar and was then distilled. There was obtained 298 g. of a fraction which distilled between 51 and 67 C. and consisted of petroleum ether and 35 g. of unreacted 3-dimethylamino-1-propyne. On continued distillation there was obtained 268 g. (74%) of 1,3,5-tris(dimethylaminomethyl) benzene which distilled at 91-175 C./15 mm. --The last portion of the distillate wa obtained under forcing conditions and was accompanied by decomposition. The residue, an intractable tar, On redistiliation the product boiled at 98-103 C./0.1 mm. and had a refractive index, 11 of 1.5058, a density, of 0.916, and a molecular refraction, MR of 80.91.

amazes On analysis, the product was found toliave-acarbon content of 7118370; a hydrogencontent of 10.99%, a nitrogen contentrof 16.42%, an equivalent weight, as determinedby titration with acid to brom phenol blue indicator end point, of 83.9, and a molecular weightof 246 as determined by an ebulliometric method in acetone. The theoretical values for the product 1,3,5-tris(dimethylaminomethyDbenzene (CisHsqNa) are: Molecular refraction, MR 79.69; carbon content, 72.25%; hydrogen content, 10.90%; nitrogen content, 16.85%; equivalent weight, 83.1 and molecular weight, 249.3. Alkaline permanganate oxidation of theproduct. produced trimesicacid which was identiiied by comparison of its. ethyl. ester with an authentiesample.

v nxmurmra 1,3,5:trisidieffiylam-mometfiybbenzene '0 A mixtureor Mgrams (0.125 mole) of 3-digram of a complex catalyst prepared. from one part of nickel carbonyl and two parts of triphenyl phosphine was heated under reflux for .fourhours while the pot temperature was maintained between 74 and 79 C. The mixture was cooled and filtered to remove one gram of tar. The filtrate was distilled to produce 10 grams of hexane, having a boiling point of 60-61 C., and 7 grams (50% of 1,3,5-tris (diethylaminomethyl) benzene which distilled'at 11'0-145" CL/1 mm. and had a refractive index, 11 of 1.5031. On redistillation the product distilled between l35145 C./0.1 mm. and had a refractive index,.,n ?,,oi. 1.5013 and .a density, (120 of 0.892, and a molecular refraction, MR of 1102. On analysis, the. product wasiound to havev an equivalent weight of. 112.5 as determined by titration to brom, phenolblue indicator, a .carbon content of.75.53%. a hydrogen content of 11.71%, and a nitrogen content of 12.51%. The product, 1,3,5-tris(diethylaminomethyl)benzene -(C21Hs9N3) has a theoretical value for molecular refraction, (MR of 107.4; for equivalent weight, of 1l1 :for carbon content, of,75.60% for hydrogen content, of 11.81%; and for nitrogen content, of 12.59%.

7 EXAMPLE 3' 1,3;-tris (dibutylaminomethyl) benzene A mixturev of. .45 g. (0.25. mole) of .3-dibuty1- .amino-lepropyne, 100 ml. .of-hexane, and 1 gram of a complex prepared from. one part of nickel carbonyl and two parts of triphenyl phosphine was heated'under reflux for four hours while the pot temperature was maintained between 70" and 76 0. Themixturewas then cooled'and filtered to remove one-gram of tar. The filtrate was distilled to obtain 59 g; of hexane which distilled at 60-64 C. and 13.5 g. (35%) of 1,3.5-tris- (dibutylaminomethyl)benzene which distilled at 168-270 C./0.4-0.8 mm. The trap collected 5 grams of unreacted 3-dibutylamino-1-propyne. The product redistilled at 200-225 C./0.25 mm. and had a refractive index, n of 1.4907, a density, @20 of 0.885, and a molecular refraction, MR of 164.1, and on analysis was found to have a nitrogen content of 8.13%. The theoretical values for the product l,3,5-tris(dibutylaminomethyl)benzene (CsaHeaNs) are: Molecular refraction, MR 162.8 and nitrogen content, 8.36%.

EXAMPLE 4 1 ,3,5-tris (methylnonylaminomethyl) benzene A mixture of 45 g. (0.23 mole) of 3-(methyl- '6 nonylamino)-l-propyne, ml. of hexane. and one gram of. av complex. catalyst. prepared from one part of nickel carbonyl: and two parts oftriphenyl phosphine was heated under reflux for four hours while the-pot temperature was held at 70 "-75-" C. 'Themixturewasthen. cooled and filteredto remove one gram-of tar. Thefiltrate was: distilled to produce-5'6 g. of'hexane which distilled atom-68 C. and 9 g; (23%) of 1,3,5- tris(methylnonylaminomethyl) benzene w hli ch distilled between" and 260" C./l mm. The trap collected fi g; of'unreacted 3-methylnonylamino-l-propyn'e. The product redistilled at 200--239" C.-/0.3 mm., had a refractive index, a of 1.4862, a density, da of 0.875, a molecular refraction, MR of 19226, and on analysis was found to have a nitrogenqcontentoi 7.05%. The theoretical. values for this product, 1,3,5-tris- (methylnonylaminomethyl)benzene '(Cas'H'zsNa) are: Molecular refraction, .MR J.90.5 andnitroencontent, 7.17%..

EXAMPLE 5' 1,3,5-msiN -morpholinomethyl)benzene.

A-mixture-of 63g. (05 mole) ofB-(N-morp'ho- 'lino)-1--propyne, 200 ml. of'hexane, and 0.5 g. of a complex catalyst prepared from one part of nickel carbonyl and two parts of triphenyl phosphine was heated under reflux for four hours while the pottemperature was held at 71 75 C. The mixture was cooled and filteredto remove one gram oftar. The residue was 'washed with 150 ml. of water. The undiss'olved hexane amounted to 194ml. Theaqueous layer was saturated'with potassium carbonate. The resulting organic layer was dried overanhydrous potassium carbonate and distilled. There was obtained 14 g. of unreacted 3 (N-m0r,phol ino) -l.-propyne which distilledat 5'0=-142' C./0'.3 mm; andhad a refractive index, 11 .of.,1.4750. and 13 g. (26%) of 1 ,3 ,5 -tris (N-morpholinomethyl) benzene which distilled-at 135-240 CL/1 mm. and hadarefractive index, 1 5 of 1.5379. Theproduct redistilled at 226-226 -C./0.'5 mm. andhad arefractive index, 15 9.01. 1.5440, adensity, 1120?, of 1.112, and a molecular'refraction, NER of 106.7. 0n analysis, the product proved to have a nitrogen content of 10.99%. The theoretical values for this product, 1,3,5 trisN-morphqlinomethyl)benzene (C21H33N3O3') are: Molecular refraction, ME 1.05.7 'andlnitrogen-content, 11.19%-

EXAMPLE 6 1 ,3,5-tris[1 (N -morpholz'no-) -3,3,5-trimethylhezcyl] benzene A mixture of 48 g. (0.2 mole) of 3-(N-morpholino)-5,7,7-trimethyl-l-octyne, 100 ml. of benzene, and 1 gram of a complex prepared from one part of nickel carbonyl and two parts of triphenyl phosphine was treated under reflux for seven hours while the pot temperature was maintained at 8590 C. The mixture then was cooled and filtered to remove one gram of tar. The filtrate was distilled to obtain 83 g. of benzene, 17 g. of unreacted octyne, and 20.5 g. of 1,3,5-tris[1- (N-morpholino) 3,3,5 trimethylhexyllbenzene (64%) which distilled between 200 and 340 C./1 mm. The product was redistilled at 260-309 C./0.4 mm., had a refractive index, 11 of 1.5071 and on analysis was found to have a nitrogen content of 5.30%. The theoretical nitrogen content of this product, 1,3,5-trisl1-(N-morpholino) -3,3,5-trimethylhexyllbenzene (C45H8103N3) is 5.90%.

.' EXAMPLE 7 1,3,5-tn's (1 -N- 1norpholz'no -1 -phenylmethyl) benzene A mixture of 40 g. (0.2 mole) of 3-N-morpholino-3-phenylpropyne-1, 100 g. of benzene, and one gram of a complex catalyst prepared from one part of nickel carbonyl and two parts of triphenyl phosphine was heated under refiuxfor four hours at a pot temperature of 8588 C.

EXAMPLE 8 1,3,5-tris(dimethylaminomethyl) benzene A nickel carbonyl-triphenyl phosphine (1:1) complex, prepared by adding 0.25 g. of triphenyl phosphine in 10 g. of benzene to 0.3 cc. of nickel carbonyl in 10 g. of benzene, was diluted with 200 ml. of petroleum naphtha having a boiling range of 60-71 C. and 83 g. (1.0 mole) of 3-dimethylamino-l-propyne. At the start the reaction was exothermic and required cooling. The mixture was heated under reflux for four hours, cooled, and filtered to remove about one gram of tar. The filtrate was distilled. There was obtained a mixture of naphtha, benzene, and 40 g. of unreacted propyne which distilled at 63-78 C. and 29 g. of 1,3,5-tris(dimethylaminomethyl)benzene (a yield of 60%) which distilled at 1l4-155 C./1.0 mm. and had a refractive index, n of 1.5102. The residue weighed seven grams.

EXAMPLE 9 1,3,5-tris(dimethylaminomethyl) benzene A nickel carbonyl-tripheny1 arsine (1:2) complex in benzene solution was prepared by adding 12.24 g. (0.04 mole) of triphenyl arsine in 25 ml. of benzene to 0.02 mole of nickel carbonyl in 25 ml. of benzene. Two m1. of the resulting solution was used to catalyze the trimerization of 16.6 g. (0.2

mole) of 3-dimethylamino-1-propyne in 25 g. of benzene in a manner described above. There was obtained on distillation benzene and 10.5 g.

of unreacted propyne which distilled at 79-81 8 -Weclaim:'

1. Compounds of the formula RNR where R and R are monovalent hydrocarbon groups when taken individually having a total of not over twelve carbon atoms and when taken together form a saturated divalent chain from the class consisting of --CH2CH2CH2CH2, --CH2CH2CH2CH2CH2, -CH2CH2OCH2CH2,

and CH2CH2SCH2CH2, said chain forming a fiveto six-sided heterocycle with the nitrogen, and R and R, represent a member of the class consisting of hydrogen and monovalent hydrocarbon groups containing not over eleven carbon atoms.

2. A compound of the formula (CHOzNCHz- REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name "Date 2,220,834 Bruson et a1. Nov. 5, 1940 2,273,141 Reppe et al Feb. 17, 1942 OTHER REFERENCES Reppe et al.: Annalen, vol. 560, pages 104-116 (1948).

Copenhaver et al.: Acetylene and Carbon Monoxide Chemistry, Reinhold Publishin Co., New York, N. Y., 1949, page 169. 

1. A COMPOUNDS OF THE FORMULA 